Packages of self-propelling atomizing low pressure liquid compositions



April 17, 1956 MlNA ET AL 2,742,321

PACKAGES 0F SELF-PROPELLING ATOMIZING LOW PRESSURE LIQUID COMPOSITIONSFiled July 27, 1955 PACKAGES OF SELF-PROPELLING ATOMIZING LOW PRESSURELIQUID COMPOSITIONS Francis A. Mina, Princeton, and Henry F. Antczak,Nixon, N. J., assignors to Chemway Corporation, a corporation ofDelaware Application July 27, 1955, Serial No. 524,781

9 Claims. (Cl. 299-95) The present invention relates to packages ofself-propelling low pressure liquid compositions, and to the nature ofsuch liquid products contents thereof which permits delivery ineffectively atomized form. More particularly, it relates to packages ofsuch compositions which comprise a water-containing alcoholic liquidmedium and a propellant dissolved in the medium, and dispensation of thecompositions.

This application is a continuation-in-part of application Serial Number427,688, filed May 5, 1954, now abandoned, which was acontinuation-in-part of application Serial Number 360,688, filed June10, 1953, now abandoned.

Previously it has been proposed to package in ampules a self-propellingliquid composition consisting of an organic liquid medium, a scent orodorous substance dissolved therein and methyl chloride propellant.However, such preparations have not proved to be satisfactory because ofunpredictable and erratic variations in and excessiveness of pressureswhich prevent safely packaging in frangible containers of limitedstrength; insufficient fineness of spray particles when limited amountsof propellant were employed in an effort to improve the safetycharacteristics; flammability and toxicity. With limited amounts ofmethyl chloride propellant to reduce the pressures the liquidcomposition delivers from small orifices in streams several feet inlength of either a continuous nature or as an in-line stream of coarsedrops, rather than as an atomized mist. A degree of atomization of suchliquid composition may be attained by increasing the methyl chloride toan amount constituting about half of the liquid composition but then thepressures become too high to permit safe packaging in frangiblecontainers, such as glass bottles, and high percentages of propellantgive to the atomized product an unduly high rate of evaporation which isunduly chilling to ones skin and is disagreeably uncomfortable. Also inlarge quantities the propellant may prove to be quite irritable andexcessively toxic to the body tissues.

A general object of the present invention is to provide unique packagesof liquid compositions of matter which permit unusually safe packagingof self-propelling watercontaining alcoholic liquid compositions of thepropellantin-product type in frangible containers, the effectivepackaging thereof permitting when desired enhanced appearance of thecontainers and contents and desired atomized delivery of the latter; thepreparation and packaging of such liquid products being economicallypracticable on a mass production basis involving automatic filling andclosing machinery, the resulting packages assuring to the customersproper safety as to potential injury from container fragments and alsowhen required as to flammability and toxicity of contents; the problemsattendant upon prior art packaging, such as those discussed above, beingefficiently solved or eliminated by the present invention.

A more specific object of the present invention is to 2,742,321 PatentedApr. 17, 1956 provide such propellant-in-product liquid compositions andto fill self-delivery containers therewith, the liquid compositionsbeing characterized by a water-containing alcoholic liquid medium whichmay serve as a carrier and/or dispensable product, if desired a solutesoluble in or miscible with the alcoholic liquid medium which may be aparticular product to be dispensed or an additive to that constituted bythe alcoholic medium, and a certain propellant selected from a specificgroup hereinafter particularized, the selected propellant being insolution in the alcoholic medium in certain definite proportions toassure unusually low internal pressures in the containers whilepermitting efiicient self-propulsive delivery with etfective atomizationin the nature of a mist of fine particles or minute droplets.

Another object of the present invention is to permit safe packaging andmarketing of liquid contents of the water-containing alcoholic type infrangible containers, such as glass bottles, while attaining, ifdesired, certain clarity and pleasing appearance of the liquid productsin such containers when transparent, effectively free of cloudiness bothof a permanent character, generally termed milkiness, and of a transientcharacter of the type wherein small globules of propellent liquid mayfloat and swirl about in the body of liquid medium when the container isshaken, soon to collect and separate out into a defined separate strata,such as a pool, in the bottom of the container when the propellant is ofgreater specific gravity or as a stratum on the top of the liquidcontents when the propellant is of lower specific gravity.

A further object of the present invention is to provide in such packagesa water-containing alcoholic liquid medium or composition, which may bein the form of a cologne containing odor material, such as perfumeemitting an agreeable odor, or in the form of other cosmeticpreparation, or topical remedy, the liquid composition being of aself-propellent nature, confinable in relatively weak containers, suchas glass bottles, under unusually low pressures which may becharacterized by a brilliantly clear and sparkling appearance, thecomposition being, when desired, relatively non-flammable or at leastnot dangerously flammable, free of dangerous toxicity, and pleasant infeeling when applied to a persons skin.

An additional object of the present invention is to provide a pushbutton package of self-propelling liquid composition, such as a cosmeticpreparation, or equivalent preparation herein indicated, containing analcoholic medium of saturated aliphatic monohydric alcohol containingnot more than three carbon atoms and having a water content; a solutesoluble in or miscible with the Watercontaining alcoholic medium whichsolute may be an agreeable aromatic substance; and a certain propellantselected from the group consisting of fluorinated, chlorinated andfluorinated low molecular Weight saturated aliphatic hydrocarbonscontaining not more than two carbon atoms, butane, and mixtures thereof;in certain critical concentrations and proportions.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the apparatus or package embodyingthe features of construction, combination of elements and arrangementsof parts, and the product contents thereof which possesses thecharacteristics, properties, and relation of components, all asexemplified in the detailed disclosure hereinafter set forth, and thescope of the invention will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following 3 detailed description taken inconnection with the accompanying drawing, in which:

The figure in the drawing is an elevational axial section of a packageof the present invention, featured by a glass container fitted with avalved closure having a relatively small discharge orifice, andillustrating in diagrammatic form atomized delivery of liquid contentsin the form of a fine mist when the closure valve is manipulated topermit self-propulsion of contents.

In the practice of the invention, there is produced a self-propellingliquid composition which comprises a liquid medium, constituting acarrier medium and/or dispensable product, in the form of awater-containing solution of saturated aliphatic monohydric alcoholcontaining not more than three carbon atoms and having a concentrationof at least about 75% by volume, and herein termed the solvent oralcoholic constituent of the liquid composition or preparation; ifdesired a substance to constitute a part of or the primary product to bedispensed, in solution in the alcoholic medium being herein termedsolute, i. e., it is a dispensable substance which is soluble in ormiscible with the alcoholic medium or solvent; and a low boiling pointpropellant selected from the group consisting of fluorinated lowmolecular weight saturated aliphatic hydrocarbons containing not morethan two carbon atoms, chlorinated and fluorinated low molecular weightsaturated aliphatic hydrocarbons containing not more than two carbonatoms (such fluorinated, and chlorinated and fluorinated hydrocarbonsbeing herein grouped together Within the intended meaning of theterminology fluorinated, chlorinated and fluorinated low molecularweight saturated aliphatic hydrocarbons containing not more than twocarbon atoms), butane, and mixtures thereof, in an amount by volume nogreater than that which constitutes 50% of the entire liquid compositionand preferably in a quantity which provides a substantially saturatedsolution of propellant in the water-containing alcoholic constituent ormedium at normal room temperatures, e. g., about 70 F. In all cases theliquid compositions constituting the contents of the containers of thepackages of the present invention are to contain a quantity of thepropellant no greater than 50% by volume of the liquid composition,usually from about to about 35% and preferably from about to about byvolume of the composition since in most instances such amounts willprovide the substantially saturated condition frequently essential toatomized mist delivery, and thus such liquid compositions may becharacterized as being of the propellant-in-product type asdistinguished from the product-in-propellant type where the propellantconstitutes the major constituent of the liquid composition. It wasunexpectedly found that the liquid composition contents of packages ofthe present invention which have been found to be of most practical andcommercial value, embodying product ingredients of a preferred natureemploy the propellants in amounts of about 10% to about by volume of thewhole composition in reaching a condition of substantial saturation.When a quantity of the composition of this propellant-in-product type isconfined in a see-through or transparent container with the propellantbeing present in an amount appreciably greater than that required toattain substantial saturation at normal room temperatures of thewatercontaining alcoholic medium by the propellant, the excess of thelatter gives to the package a source of hazard and also an unattractiveappearance by collecting as a discernable pool of separated propellantin the bottom of the container or as large beads thereof moving aboutthrough the product medium when the package is shaken. If in a packagein which the composition includes the alcoholic medium in the preferredor optimum alcohol concentration the quantity of the propellant presentin the container is substantially below about 6% by volume 1688 than tamount of propellant sufficient to attain exact saturation of theproduct medium by the propellant (i. e., the volume of the propellant isshort of the ideal or optimum quantity for exact saturation at aspecific normal room temperature by an amount greater than 6% of theoptimum propellant quantity) the delivery from the package orifice willnot be in the form of a desired misty spray in which the particles areof sutficient fineness, that is the fineness which is required for thedemanded mist atomization, will not be produced. Moreover, largeramounts of such propellant undesirably reduce the alcoholic constituentor product medium content which can constitute a serious economicalfactor, and when an excess free pool of propellant is provided therebylikely will cause a hazardous condition in containers of shatterablematerial, such as glass, should the latter be employed, and in someinstances such excessive amounts of propellant may cause development ofundesirably higher pressures to increase the hazard; whereas loweramounts give an improper stream or in-line large droplet delivery. Thuswhen the quantity of the propellant present is between an amount whichis about 6% less than the ideal or optimum amount for exact saturationat normal room temperature of the alcoholic medium of optimum alcoholconcentration and an amount which may be slightly in excess of the idealor optimum amount thus forming only a very small pool or stratum ofseparated propellant in the container, the product composition is hereconsidered to be a substantially saturated solution which will assurethe desired or demanded atomized mist delivery.

The optimum or preferred alcohol concentration by volume of thealcoholic medium of composition contents of these packages is about formethanol, about 88% for ethanol, and about 80% for isopropanol and itsequivalent propanol. Beyond such alcohol concentrations in therelatively small remainders of the ranges thereof up to the upper limitsset by the various requirements as hereinafter fully explained thepropellants may be employed in amounts less than those quantitiesrequired to give saturation of the alcoholic mediums appreciably greaterthan about 6%. As will be seen from the following tables suchpercentages by volume of propellants which may be employed to attain thedesired results in such upper small remainders of the ranges will varyup to about 31% by volume. In other words, as one approaches the upperlimit of the range of alcohol concentration for any particular alcoholicmedium the quantity of the propellant which will provide acceptable mistdeliveries may be below that for exact saturation of the alcoholicmedium at these alcohol concentrations in progressively largerquantities but no less than 69% by volume of the quantity required forexact saturation. This appears to be due to the fact that as the alcoholconcentration by volume is raised, i. e., the water content is reduced,increasingly greater quantities of the propellant are required to reachthe point of exact saturation and in the upper portions of the ranges ofalcohol concentration the quantity of propellant which will. assureproper atomized mist delivery will have been added to the compositionappreciably before the quantity necessary to exact saturation of thealcoholic medium has been incorporated. There is physically present inthe composition a large enough quantity of propellant to assure atomizedmist delivery of the alcoholic medium in such high alcoholconcentrations even though the quantity of propellant present isappreciably below that amount which will go into solution in thealcoholic medium to attain saturation thereof. The following tablesillustrate this feature of variation from exact saturation of thealcoholic medium by the propellant, the particular propellants selectedbeing typical and those preferred for commercial practice of theinvention. The following figures are given on the basis of one hundredparts by volume of the liquid composition forming the contents of acontainer of a package of the present invention.

Table A Parts by vol- Minimum ume of parts by voli gig gz g (CClFzh umeof the to enant Alcohol concentration by (Freon 114) propellant to p tvolume of alcoholic medium propellant to provide satf ow amoun ecessaryfor saglurlate a1 isfactorsirz exact Satura co to mespray pa o dium at10 F. tern at 70 (I) Methanol:

Table B Parts by vol. Percent of prop. mix. Min. parts diff. of

[CCI2F210 by vol. of prop. below Al. cone. by vol. of parts by Wt. prop.to give amount a1. med. (C CIFg) 90 satisfactory necessary parts by wt.]spray for exact to sat. a]. pattern sat. at med. at 70 F. 70 F.

(I) ethanol:

92% (optimum) 21.8 20. 7 5.05 95% 39 30. 5 21. 8 96 27 43. 4 34. 5 22.3O O 5 36. 2 (II) Ethanol: 27 6O 87% (optimum) 21.9 20. 7 5. 48 87.5%23. 5 21. 9 (i. 81 26. 5 24. 2 8. 68 33. 5 30. 5 8. 96 49 39. 0 20. 41

77% (optimum). 29. 5 28. 5 3. 39 80% 39. 2 34. (i 11. 73 85% 50 39 22.00

Further it has been found that the alcohol concentration of thewater-containing alcoholic medium or constituent has a critical lowerlimit due to the fact that with alcohol concentrations appreciably lessthan 75% by volume, i. e., containing appreciably more than 25% water,the solubility of the particular propellant therein is reduced markedlyso that the compositions have neither the desired appearance norcapability of forming an atomized spray, i. e., in which the particlesare of suflicient misty fineness. An additional advantageouscharacteristic of the present liquid compositions is that only unusuallylow pressures are generated in the containers which are, at about 70 F.,not in excess on 25 p. s. i. g., and usually in the range of about ll to15 p. s. i. g., which is of especial import when the compositions arepackaged in relatively weak or frangible containers, such as glassbottles.

The water-containing alcoholic constituent of the liquid composition ordispensable preparation which is utilized in the practice of the presentinvention may be methanol, ethanol, isopropanol and its equivalentpropanol, and mixtures thereof; ethanol being particularly desirable.Further, it has been determined that the miscibility of the propellantin the alcohol is directly proportional to the number of carbon atoms ofthe alcohol, thus the miscibility increases from methanol containing one(1) through ethanol containing two (2) to isopropanol and its equivalentpropanol containing three (3) carbon atoms, and also that the lowerlimit of alcohol concentration by volume for methanol is about 90%, forethanol about 85%, and for isopropanol and its equivalent propanol about75%. The present invention is concerned only with packages ofself-propelling liquid compositions of the propellant-in-product type inwhich the product comprises or consists of an alcoholic constituent ormedium having an appreciable water content and the propellant is one ofthose set forth herein. Thus, perhaps it would be just as well to speakof the water concentration of the water-containing alcoholic constituentor medium as of the alcohol concentration. In either view research hasestablished that a critical point in the upper limit of alcoholconcentration or lower limit of water concentration of thesewater-containing alcoholic mediums or solutions appears to be reachedrespectively between 96 and 97% by volume alcohol concentration theequivalent of which is between 3 and 4% by volume water concentration.With any of the mentioned saturated aliphatic monohydric alcoholscontaining not more than three carbon atoms when the alcoholconcentration of the water-containing alcoholic medium is below 97% byvolume, i. e., its water concentration is above 3% by volume, layeringoccurs in which propellant separates out of the alcoholic medium orproduct solution unless the relative proportions by volume of thepropellant and product are adjusted so that the propellant is present inan amount no greater than that established amount which provides atnormal room temperatures saturation of the water-containing alcoholicmedium by the propellant. The appreciable water content in aconcentration of more than 3% by volume but no greater than the hereinindicated upper limit is the means whereby the employed amount of thespecified propellants may be limited or reduced to effect an economy ofuse of the relatively expensive propellant ingredient while permittingattainment of desired atomized mist delivery. The greater the watercontent between the limits established by the present invention forthese various alcohols, the lesser is the amount of the particularpropellant selected from the specified group which will go into solutionin the water-containing alcoholic medium. By using greater amounts ofwater within the limits herein established the amounts of the particularpropellant ingredient selected from the recited group to attainsubstantial saturation of the water-containing alcoholic medium can bereduced. In using increased amounts of water for this purpose withsuitable adjustments of the volumes of the selected propellant to avoidlayering one must remember and fulfill the requirement that the volumeof propellant is to be such as to satisfy the primary need for anddemand of an acceptable delivery of the liquid produce in the form of anatomized mist or fine spray free from coarse drops and streaming. Forexample, with water-containing methanol alcoholic medium of an alcoholconcentration of 96.5% by volume, i. e., a water concentration of 3.5%by volume, about 50% by volume of dichlorotetrafluoroethane propellantwill go into solution therein and the alcoholic medium will besubstantially saturated with the propellant to give an atomized mistdelivery at normal room temperature. If the alcohol concentration of thewater-containing methanol is reduced to 96% by volume by use of 4% byvolume of water about 38% by volume of the dichlorotetrafiuoroethanepropellant will go into solution therein to give a good spray pattern ofatomized mist under like conditions. In substituting water-containingethanol for the methanol alcoholic medium it has been found that as muchas 50% by volume of dichlorotetrafiuoroethane propellant would go intosolution in the water-containing ethanol medium having an alcoholconcentration of about 93% by volume, i. e., a water concentration ofabout 7% by volume, to attain saturation of the alcoholic medium whichit has been observed assures the atomized mist delivery at normal roomtemperature that was desired. Satisfactory atomized mist spray patternsunder like conditions are attained at alcohol concentrations of thewater-containing ethanol medium of 94% and 95% by volume as well as atthe 93% by volume alcohol concentration, but values of the latter above95 by volume result in unsatisfactory spraying of thepropellant-in-product composition in the form of a central streamflanked by coarse drops with the central stream breaking up into coarsedrops at a distance of about six feet (6') from the outlet orifice ofthe package spray head. When isopropanol or its equivalent propanol wassubstituted for the methanol or the ethanol it was found that as much as50% by volume of the dichlorotetrafluoroethane propellant would go intosolution in the water-containing isopropanol or propanol medium havingan alcohol concentration of about 85% by volume, i. e., a waterconcentration of about 15% by volume, saturation of the alcoholic mediumby the propellant being attained at that point and assuring the desiredatomized mist delivery. Good spray patterns under like conditions areattained at alcohol concentrations by volume of the water-containingisopropanol and propanol mediums of 86%, 87% and 88% in addition to thatat the 85% by volume alcohol concentration, but isopropanol and propanolalcohol concentrations above 88% by volume cause thepropellant-in-product composition to be delivered from the package sprayhead orifice in the form of a coarse drops-flanked stream about six feet(6') long which breaks up at that distance into coarse drops. The lowerlimits of the ranges of the concentrations by volume of the fouralcohols to be used in the practice of the present invention aredictated chiefly by the spray patterns. At alcohol concentrations belowabout 75 by volume of isopropanol and propanol, below about 85% byvolume of ethanol and below about 90% by volume of methanol when thewater-containing alcoholic mediums are saturated with the selectedpropellants the deliveries of the compositions from the packages areweak sprays of coarse drops since there is insufficient propellant insolution to explode the released compositions into strong sprays ofatomized mist.

When a mixture of dichlorodifluoromethane and dichlorotetrafiuoroethane,such as 10 parts by weight of CC12F2 (Freon l2) and 90 parts by weightof (CClF2)2 (Freon 114), is substituted as the propellant for thedichlorotetrafluoroethane a somewhat similar pattern of alcoholconcentrations to give a proper atomized mist delivery is experienced.In the event that water containing methanol is employed as thewater-containing alcoholic medium an alcohol concentration of about96.2% by volume will take into solution about 50% by volume of thepropellant mixture and a good spray pattern results at 70 F. Whenwater-containing ethanol is employed an alcohol concentration thereof ofabout 92% by volume will take up about 49% by volume of the propellentmixture to give a good spray pattern at 70 F. In the use of isopropanoland its equivalent propanol watercontaining solutions thereof will atalcohol concentrations of about 85% by volume take up about 50% byvolume of the propellent mixture to give an excellent atomized mistdelivery at 70 F. In the employment of mixtures of any two or three ofthese alcohols as the solvent or alcoholic constituent the concentrationby volume of each component alcohol will follow the pattern dictated bythe requirement of about 75% and upward to just less than 97% ofisopropanol and its equivalent propanol, about 85% and upward to justless than 97% of ethanol and about 90% and upward to just less than 97%of methanol so that the concentration by volume of the alcoholic mixturewill be of the order of that pattern. For example, if a mixture ofisopropanol (or its equivalent propanol) and ethanol be employed as thealcoholic constituent in the proportions of about equal parts, theminimum concentration by volume of the mixture will be about 80%.

It will thus be understood that in the production of packages of thepresent invention the alcohol concentration of the water-containingalcoholic medium is to be kept within certain limits to assure theattainment of the desired characteristics including the requiredatomized mist delivery in the form of a very fine strong spray of goodpattern. The use of methanol for the water-containing alcoholic mediumdictates a range of alcohol concentration of from about 90% to about96.5% by volume,

i. e., the water concentration will be in the range of about 3.5% toabout 10% by volume. If ethanol be employed in the preparation of thewater-containing alcoholic constituent the alcohol concentration thereofshould be kept within the range of about to about by volume, i. e., thewater concentration will be maintained in the range of about 5% to about15% by volume. When isopropanol or its equivalent propanol is used inmaking up the water-containing alcoholic medium the alcoholconcentration thereof should be within the range of about 75 to about88% by volume, i. e., the water concentration should be within the rangeof about 12% to about 25% by volume.

The solute which is to be dispensed should be soluble in or misciblewith the water-containing alcoholic medium in an effective amount andmay be a deodorizer, as dimethylphthalate and pine oil; a medicinalsubstance as benzoin, an anti-histamine, novocaine, procaine and ethylpara-amino benzoate; a lacquer substance, as shellac, ester gum andsynthetic resins soluble in the alcohol medium; an antiperspirant;tannic acid; umbelliferone; or an insecticide as rotenone, rotenoids anddichloro-diphenyltrichloroethane; of an odorous substance or materialemitting an agreeable or pleasant odor, and commonly termed a perfume.The perfume ingredient may be either solid or liquid and either ofnatural or synthetic origin. Thus, the perfume ingredient may be anessence of various flowers, as the rose, lavender, gardenia, carnation,lilac and lily-of-the-valley; and irone and other synthetic odoroussubstances, for example, geranyl acetate, eugenyl acetate, phenyl alkylethers, as phenyl ethyl ether and esters as methyl salicylate; and suchperfume ingredient may be one or a mixture of a plurality of suchessences in the form of essential oils.

The propulsion of the liquid composition to be atomized is chieflyeffected by means of the presence therein of the particular propellant,e. g., from about 10% to about 35% of one or more of the recitedpropellent materials, the boiling point of the propellant being atnormal atmospheric pressure lower than normal room temperatures, such asless than about 70 F. at one atmosphere. It will be realized that thepropellant may be either a single one of the recited propellentcompounds or a compatible admixture of such compounds if the mixture hassuch a boiling point, and further that the propellant shall be solublein the alcoholic preparation to be atomized.

The particular fiuorinated, and chlorinated and fiuorinated lowmolecular weight saturated aliphatic hydrocarbon propellent compoundsmay be represented generally by the formula cnHzclg Fz, wherein n is awhole number (usually 1 or 2), x is zero or a whole number, y is zero ora whole number, and z is a whole number, and the sum of x, y and z isequal to 2n-l-2. More particularly, mention may be made of thefollowing:

monochlorotrifiuoromethane, trichloromonofluoromethane,dichlorodifluoromethane, dichloromonofiuoromethane,monochlorodifiuoromethane, trichlorotrifiuoroethane,dichlorotetrafluoroethane, difiuoroethane, and difiuoromonochloroethane.The use of dichlorotetrafluoroethane has led to markedly satisfactoryresults.

Some of the herein recited propellent compounds, such astrichloromonofiuoromethane and trichlorotrifiuoroethane, boil attemperatures higher than 70 F. at a pressure of one atmosphere and thus,alone, are not practical for propellants in the practice of the presentinvention in climates where normal room temperatures, at which thepreparations are to bemist delivered, are below their boiling points.However, they are useful in propellent mixtures of the presentinvention, being utilized as pressure diluents for those propellentcompounds herein recited which have the lower boiling points and thusthe higher pressures. For example, the present invention has beensuccessfully practiced by mixing dichlorodifluoromethane withdichlorotetrafluoroethane in such proportions as to form propellentmixtures having vapor pressures below the maximum limit of near 25 p. s.i. g. under like conditions. In packages of the present invention butaneacts very similar to dichlorotetrafluoroethane wherever the greaterflammability of the former is of no importance or is blanketed to anacceptable degree by the other ingredients.

When such a liquid composition or preparation, comprising thewater-containing alcoholic constituent or solvent, the solute and theparticular propellant, is confined in indicated proportions in a closedcontainer, such as that indicated at 1 in the drawing, an internalpressure of relatively low order is created therein. Such internalpressure is of the order of about 11 to 15 p. s. i. g. at about 70 F.when the proportions of the ingredients of the liquid composition are ofthe order herein taught. That is an important safety factor particularlywhen frangible containers, such as glass, are employed as indicated inthe drawing. Appearance and economy dictate the desirability of usingfor packaging many products in transparent containers, such as thoseformed of clear glass and certain see-through synthetic plastics, e. g.,polystyrene and the like, but a tendency for some such materials toshatter when subjected to blows, such as when dropped, with attendanthazard of jagged pieces and slivers thereof to fly about under thedriving force of the internal pressure, demand that the latter be keptbelow a safe maximum, and preferably in the range of about 11 to 15 p.s. i. g. at normal room temperatures. Safe pressures may be somewhathigher, such as up to about to p. s. i. g., particularly where strongeror suitably protected containers are employed; and lower pressures, e.g., 10 p. s. i. g., may be suitable for proper propulsive delivery ofthe products in atomized form when certain types of ingredients are usedin certain proportions within the scope of the present invention.

Reducing the amount of propellant by increasing the water content of thealcoholic medium within the specified limits while limiting thepropellant to that quantity which will go into solution in thewater-containing alcoholic medium under particular conditions and atnormal room temperature does not materially alter the internal pressureof the package. Increased amounts of water with attendant decrease inthe amount of propellant through the entire specified range for theparticular watercontaining alcohol being used will at most cause adecrease in the internal pressure within the package of only a few p. s.i. The maximum internal pressure is that of a confined body of theselected propellant alone and that of any particular package of thepresent invention wherein the propellant is in solution in thewater-containing alcoholic medium is from a few p. s. i. below thatmaximum up near and closely approaching the latter. I. C. C. regulationspermit such packaging and distribution in frangible and relatively weakcontainers, such as glass bottles, when their internal pressures are nogreater than or are kept below 25 p. s. i. g. at 70 F. This dictatesthat the maximum internal pressures of the packages of the presentinvention no greater than 25 p. s. i. g. which in turn dictates in partthe selection of the propellant. No low boiling point liquid can serveas a propellant in a package of the present invention if the packagedcomposition containing it can develop when confined under normalconditions a pressure in excess of 25 p. s. i. g. at 70 F. It is thusbest to select such propellants for use with this invention as havevapor pressures no greater than 25 p. s. i. g. at 70 F. and otherrequirements of the present invention dictate its selection from thespecified group consisting of flourinated, chlorinated and fiourinatedlow molecular weight saturated aliphatic hydrocarbons containing notmore than two carbon atoms; butane; and mixtures thereof.

The present invention is concerned chiefly with factors of appearance ofthe products when packaged in transparent or see-through containers,safety when the containers are of frangible and potentially dangerousshatterable character, and particularly efiicient delivery in atomizedform in the nature of a cloud or mist of very fine particles or minutedroplets; and not with any particular improvements in designs ofdelivery apparatus. For example, the glass bottle 1 illustrated in thedrawing is equipped with conventional delivery equipment in the form ofanchoring cap means 2 which holds in position mounting means for aneduction or dip tube or stand pipe 3 serving as a gas-tight closure forthe bottle and a discharge valve and nozzle assembly 4 showncommunicating with the duct provided by the tube. The valve and nozzleassembly 4 is illustrated not by way of dictating any particulardelivery apparatus since many conventional types have been found to besuitable.

As is well understood in this art and as shown, the bottom end 5 of theeduction tube 3 extends to near the bottom 6 of the container 1 toassure a delivery of a maximum amount of the body 7 of contained liquidcomposition, the latter, however, being unique as to ingredients andproportions thereof in accordance with the present invention. Thedischarge passage leading from the container 1 includes the ductprovided by the eduction tube 3 and a passage portion 8 of no particulardesign extending through the nozzle assembly 4 to a relatively smalldischarge orifice 9, with a biased valve 10 controlling flow through thenozzle passage portion. Conventional spray heads for such types ofpackages have outlet or discharge orifices of the order of 0.018" to0.019" in diameter (which may vary from about 0.015" to 0.020" in dia.);and conventional aerosol practices allow orifices thereof to be of asize within the range of about 0.005" to 0.025 in diameter dependingupon the viscosity of the product to be dispensed and othercharacteristics of the packages. The discharge passage may be ofsubstantially uniform cross-section throughout up to the dischargeorifice, and experience has taught that with certain compositions of thepresent invention, such a simplified uniform discharge passage may giveimproved atomization.

When the valve 10, normally biased to closed position, is opened, suchas by manual manipulation or finger depression, the internal pressure inthe container 1, due to the vapor pressure of the particular low boilingpoint propellant in solution in the water-containing alcoholic medium orsolvent, and possibly due to some extent to that of the alcohol of thelatter in gaseous phase with the propellent vapors in the gas head abovethe body of liquid 7, forces the liquid composition out through thedischarge passage past the valve 10 to be delivered as an atomized sprayor mist from orifice 9, as diagrammatically indicated at 11, and not asa long stream of substantially continuous form or substantially in-linelarge drops. This desired atomization is effected without the employmentof excessive and unsightly separated amounts or pools of containedpropellant and without the employment of dangerously high internalpressures of the order of 40 p. s. i. g. at normal room temperatures ofabout 70 F.

The packaged product presents an attractive, sparklingly bright andclear appearance through the transparent or see-through container, andin order to assure maintenance of such desirable estheticcharacteristics, the propellent ingredient of the composition preferablymay be employed in an amount near but slightly less than the ideal oroptimum amount required for complete or exact saturation of thesolute-containing alcoholic medium by the propellant, and within theranges of variations indicated above. Thus, at normal room temperaturesof the order of about 70 to F. clarity is attained; and even at somewhatreduced temperatures, such as down to about 65 F., there is littletendency for some of the propellant in solution in the water-containingalcoholic medium to separate out of the composition. By incorporatingsuch amounts of the specified propellent ingredient an internal pressureof safe order, which will give the desired atomized delivery, isassured. Of course, at elevated temperatures up to about 130 F., thestandard test maximum, the clarity in appearance and the atomizeddelivery are maintained since the amounts of propellant soluble in thesolute-containing medium to saturation increases with temperature, andthe atomizing characteristics are progressively enhanced. Thepropellants here proposed assure another important safety factor. Thepressuretemperature relationship curves curve down away from obliquestraight lines to progressively greater degrees approaching thehorizontal with progressive increases in temperature. This is markedlycharacteristic of dichlorotetrafiuoroethane (Freon 114) which due to thenonflammability thereof and freedom from tendency to irritate human skinis particularly desirable for use in practicing certain phases of thepresent invention.

If the liquid contents of a package of the present invention were in thenature of a product-in-propellant composition, or the liquid compositionwas confined in the container with a pool of free excess propellantseparated from the product medium sudden release of the contents fromconfinement, such as may attend breakage of the container, would beaccompanied by prompt and vigorous boiling of the liquid propellant tovapor phase, thus rapidly converting potential energy to kinetic energywith a minimal lag. If the liquid composition is of the type hereintaught, i. e. propellant-inproduct where the product medium constitutesat least half by volume of the composition or the major constituent inwhich the propellant is dissolved, and there is no appreciable amount ofpropellant collected as free excess in a separate pool or stratum,sudden release from confinement by the container results in only slowretarded boiling to vapor phase with checked transition from potentialforce to kinetic force through an appreciable lag phase. If thecontainer be of shatterable material, such as glass, and the liquidcontents be of the latter type of propellant-in-product with noappreciable excess pool of propellant, fragments of the broken containerwill be propelled with minimum danger only by the force of the internalpressure caused by the vapor phase propellant in the gas head; and bythe time the propellant slowly boils out of the product medium orwater-containing alcoholic constituent the force of the gas headpressure propulsion of fragments will be spent and slow boiling ofpropellant dissolved in the product medium with attendant slow change ofpotential force to kinetic energy will be harmless and incapable ofdangerously supplementing the gas head drive of fragments.

As an illustrative embodiment of a manner in which the invention may bepracticed, the following examples are presented. The parts are byvolume.

Example I Ethanol (87% alcohol concentration) 75 parts by volume.Dichlorotetrafiuoroethane parts by volume. Perfume Q. s. (sufiicientquantity). Package in a valved container having a dip tube.

Example II A composition suitable for the deodorization of air may beprepared in the following manner: Mix 1 gm. of perfume oil and 0.5 gm.of diethyl phthalate into 85 ml. of isopropanol and add water q. s. to100 ml. to form an alcoholic medium. To 52 ml. of this alcoholic mediumin a closed valved container having a dip tube add 48 ml. ofclichlorotetrafiuoroethane to form a pressurized package.

Example III A composition may be prepared containing 98 ml. of ethanolof an alcohol concentration of 95%, 2 gms. of ethyl p-amino benzoate,perfume q. s., and water q. s. to 100 ml. To this Water-containingalcoholic medium may be added dichlorotetrafiuoroethane in the relative12 proportion of 30 parts to 70 parts by volume within a valvedcontainer having a dip tube.

Example lV Another cosmetic preparation may be packaged as a variationof Example I by utilizing as the propellant 12.5 parts by volume ofdichlorotetrafiuoroethane and 12.5 parts by volume of butane, with whichis mixed parts by volume of ethanol of an alcohol concentration of about87% and perfume q. s. which may be a fraction of 1% to a few per cent.Also butane may be substi tuted wholly for the dichlorotetrafiuoroethaneof Example I.

Example V There may be substituted for the propellant ingredient of anyof the above examples a propellant admixture ofdichlorotetralluoroethane, dichlorodifiuoromethane andtrichlorotrifiuoroethane in the relative proportions by weight,respectively, of about 23%, about 15.5% and about 61.5%, and in thequantities by volume indicated in these examples. Such an admixturepropellant has a pressure of about 17 p. s. i. g. at about 70 F.

Example VI An antiseptic aerosol tincture may be packaged by adding to92 ml. of ethanol 0.2 gm. benzalkonium chloride and water q. s. to 100ml. to form an alcoholic medium. 52 m1. of the alcoholic medium ishoused with 48 ml. of (Freon 114) dichlorotetrafluoroethane in a valvedcontainer having a dip tube. 48 ml. of 10 parts by weight of Freon 12and parts by weight of Freon 114 may be substituted for the Freon 114.

Example V11 T0 92.3 ml. of ethanol add 2 gms. perfume oil and water q.s. to ml. House 52% by volume thereof with 48% by volume ofdichlorotetrafiuoroethane in a valved container having a dip tube.

The present invention is particularly important to the production,marketing and use of cosmetic preparations, such as colognes,deodorizers, and antiperspirants, as well as tinctures, etc. Forexample, it has been found to be highly advantageous to the marketing ofself-propulsive colognes in attractive, push button or valved glassbottles having eduction or dip tubes. Example 1 above is well suited tothe latter purpose and the q. 5. (quantity sufficient) amount of theconcentrated perfume essence may be of the order of about 2% by weightof perfume-containing alcoholic medium; a fraction of one percent, e.g., about 0.5% being suitable when highly odorous material is employedas the perfume ingredient; but of course when desired greaterquantities, e. g., up to about 8% by weight of perfume oil, may beemployed.

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description, are efficiently attained and,since certain changes may be made in the constructions or packages setforth and the contents of the containers thereof without departing fromthe scope of the invention, it is intended that all matter contained inthe above description or shown in the accompanying drawing shall beinterpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which, as amatter of language, might be said to fall therebetween.

Particularly it is to be understood that in said claims, ingredients orcompounds recited in the singular are intended to include compatiblemixtures of such ingredients wherever the sense permits.

Having described our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly awater-containing alcoholic medium of saturated aliphatic monohydricalcohol selected from the group consisting of methanol, ethanol,isopropanol and its equivalent propanol, and mixtures thereof, having awater concentration greater than 3% by volume, the alcohol concentrationof said alcoholic medium being by volume from about 75% to about 88% forisopropanol and its equivalent propanol, from about 85% to about 95% forethanol and from about 90% to about 96.5% for methanol; said propellantbeing selected from those of the group consisting of fluorinated lowmolecular weight saturated aliphatic hydrocarbons having a carboncontent of C1-C2, chlorinated and fluorinated low molecular weightsaturated aliphatic hydrocarbons having a carbon content of C1-C2,normal butane, and mixtures thereof, which have a boiling point at oneatmosphere lower than normal room temperatures and a vapor pressure upto 25 p. s. i. g. at 70 F.; said propellant being present in said liquidcomposition in an amount up to 50% by volume thereof and from about 69%by volume of that quantity which provides a saturated solution of thealcoholic medium at normal room temperatures to that quantity whichprovides such saturation, the amount of said propellant in solution insaid alcoholic medium being at least that quantity which provides at theselected alcohol concentration of said medium atomized mist delivery ofthe dispensable product solution at normal room temperatures.

2. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein 9. body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly awater-containing alcoholic medium of saturated aliphatic monohydricalcohol selected from the group consisting of methanol, ethanol,isopropanol and its equivalent propanol, and mixtures thereof, having awater concentration greater than 3% by volume, the alcohol concentrationof said alcoholic medium being by volume from about 75% to about 88% forisopropanol and its equivalent propanol, from about 85% to about 95% forethanol and from about 90% to about 96.5% for methanol; said propellantbeing selected from those of the group consisting of fluorinated lowmolecular weight saturated aliphatic hydrocarbons having a carboncontent of C1-C2, chlorinated and fluorinated low molecular weightsaturated aliphatic hydrocarbons having a carbon content of C1-C2,normal butane, and mixtures thereof, which have a boiling point at oneatmosphere lower than normal room temperatures and a vapor pressure upto 25 p. s. i. g. at 70 F.; said propellant being present in saidalcoholic medium in an amount constituting from about 10% to about 35%by volume of the liquid composition with the amount of propellant insolution being from about 23% less than and up to about that quantitywhich provides at normal room temperature a saturated solution thereofin the alcoholic medium, the amount of said propellant in solution insaid alcoholic medium being at least that quantity which provides at theselected alcohol concentration of said medium atomized mist delivery ofthe dispensable product solution at normal room temperatures.

3. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly awatercontaining alcoholic medium of saturated aliphatic monohydricalcohol selected from the group consisting of methanol, ethanol,isopropanol and its equivalent propanol, and mixtures thereof, having awater concentration greater than 3% by volume, the alcohol concentrationof said alcoholic medium being by volume from about 75 to about 88% forisopropanol and its equivalent propanol, from about to about 95% forethanol and from about 90% to about 96.5 for methanol; said propellantbeing dichlorotetrafluoroethane present in said liquid composition in anamount up to 50% by volume thereof and from about 69% by volume of thatquantity which provides a saturated solution of the alcoholic medium atnormal room temperatures to that quantity which provides suchsaturation, the amount of said propellant in solution in said alcoholicmedium being at least that quantity which provides at the selectedalcohol concentration of said medium atomized mist delivery of thedispensable product solution at normal room temperatures.

4. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly awatercontaining alcoholic medium of saturated aliphatic monohydricalcohol selected from the group consisting of methanol, ethanol,isopropanol and its equivalent propanol, and mixtures thereof, having awater concentration greater than 3% by volume, the alcohol concentrationof said alcoholic medium being by volume from about 75% to about 88% forisopropanol and its equivalent propanol, from about 85% to about 95% forethanol and from about 90% to about 96.5% for methanol; said propellantbeing dichlorotetrafiuoroethane present in said liquid composition anamount up to 50% by volume thereof and from about 6% less than and up toabout that quantity which provides at normal room temperature asaturated solution of dichlorotetrafluoroethane in the alcoholic medium,the amount of said propellant in solution in said alcoholic medium beingat least that quantity which provides at the selected alcoholconcentration of said medium atomized mist delivery of the dispensableproduct solution at normal room temperatures.

5. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly aWater-containing alcoholic medium of ethanol having an alcoholconcentration from about 85% to about 95% by volume; said propellantbeing dichlorotetrafluoroethane present in said ethanol alcoholic mediumin an amount constituting from about 16.5% to about 35.5% by volume ofthe water-containing ethanol and dichlorotetrafiuoroethane content, theamount of said propellant in solution in said alcoholic medium being atleast that quantity which provides at the selected alcohol concentrationof said medium atomized mist delivery of the dispensable productsolution at normal room temperatures.

6. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution consisting of awater-containing alcoholic solvent of ethanol having an alcoholconcentration of about 88% by volume, and an alcoholsoluble solute of aperfume ingredient in solution in said solvent in an effective amountand up to about 8% by weight of the dispensable product solution; saidpropellant being dichlorotetrafiuoroethane present in said liquidcomposition in an amount from about 23% to about 24% by volume of thesolvent and dichlorotetrafiuoroethane content.

7. A package of self-propelling propellant-in-product liquid compositioncomprising, in combination, a hermetically sealed glass container havinga valved outlet terminating in a relatively small discharge orifice andan eduction tube leading to the valved outlet from a point near thebottom of said container, and a body of liquid composition consistingessentially of Water-containing ethanol solvent having an alcoholconcentration of about 85% to about 95% by volume, a dispensable productalcohol-soluble solute in solution in the solvent, and a propellant ofdichlorotetrafluoroethane in an amount constituting from about 16.5% toabout 35.5% by volume of the solvent and dichlorotetrafiuoroethanecontent; said dichlorotetrafluorethane propellant being in solution insaid solute-containing solvent in an amount from about 6% less than andup to about that quantity which provides at normal room temperature asaturated solution of dichlorotetrafiuoroethane in said solvent, theamount of said propellant in solution in said alcoholic medium being atleast that quantity which provides at the selected alcohol concentrationof said medium atomized mist delivery of the dispensable productsolution at normal room temperatures; said body of liquid compositionbeing confined in said container under the vapor pressure of thepropellant which at normal room temperatures is about 11 p. s. i. g. toabout 15 p. s. i. g.

8. A package of relatively low pressure, self-propelling liquidcomposition comprising, in combination, a fluid tight container oflimited strength; means providing a relatively small discharge orificefor atomized dispensation of contents and an openable closed passageleading to said discharge orifice from the interior of said container ata point near the bottom thereof; and a con tained two-phase fluid systemconfined in said container at a pressure of from about 11 p. s. i. g. toabout 15 p. s. i. g. at normal room temperatures, said system consistingof a body of propellant-in-product liquid composition having aWater-containing alcoholic constituent as a solvent, a dispensableproduct alcohol-soluble solute in solution in the solvent and apropellant in solution in the solute-containing solvent, and a gas headcomprising some of the propellant and solvent in vapor phase; thesolvent being ethanol having an alcohol concentration from about 85 toabout 95 by volume; said propellant being dichlorotetrafluoroethane withthe amount thereof in said container constituting from about 16.5 toabout 35.5 by volume of the solvent and dichlorotetrafluorethane contentand from about 6% less than and up to about that quantity which providesat normal room temperature a saturated solution ofdichlorotetrafiuoroethane in said solvent, the amount of said propellantin solution in said alcoholic medium being at least that quantity whichprovides at the selected alcohol concentration .of said medium atomizedmist delivery of the dispensable product solution at normal roomtemperatures.

9. A package of relatively low pressure, self-propelling liquidcomposition comprising a fluid-tight container having closure meansproviding a small discharge orifice for atomized dispensation ofcontents and a valve-controlled passage leading to said dischargeorifice from the interior of said container at a point of immersion inthe liquid composition, said container confining therein a body ofliquid composition for delivery through the orifice in liquid phaseconsisting essentially of a liquid mixture of dispensable productsolution and volatile propellant and being of the propellant-in-producttype which immediately upon orifice delivery will be converted to anatomized mist by change of the contained propellant from liquid togaseous phase, the body of liquid composition being confined in thecontainer under a vapor pressure of the propellant up to 25 p. s. i. g.at 70 F.; said dispensable product solution being chiefly aWater-containing alcoholic medium of saturated aliphatic monohydricalcohol selected from the group consisting of methanol, ethanol,isopropanol and its equivalent propanol, and mixtures thereof, having awater concentration greater than 3% by volume, the alcohol concentrationof said alcoholic medium being by volume from about to about 88% forisopropanol and its equivalent propanol, from about to about for ethanoland from about 90% to about 96.5% for methanol; said propellant being amixture of dichlorodifluoromethane and dichlorotetrafluoroethane withthe latter being present therein in such predominant amount that thepropellant mixture has a boiling point at one atmosphere lower thannormal room temperatures and a vapor pressure up to 25 p. s. i. g. at 70F., said propellent mixture being present in said liquid composition inan amount up to 50% by volume thereof and from about 72% by volume ofthat quantity which provides a saturated solution of the alcoholicmedium at normal room temperatures to that quantity which provides suchsaturation, the amount of said propellant in solution in said alcoholicmedium being at least that quantity which provides at the selectedalcohol concentration of said medium atomized mist delivery of thedispensable product solution at normal room temperatures.

References Cited in the file of this patent UNITED STATES PATENTS1,892,750 Rotheim Ian. 3, 1933 2,621,014 Eiford Dec. 9, 1952 FOREIGNPATENTS 557,259 Germany Aug. 20, 1932 OTHER REFERENCES 15 tion 1949),pp. 1922, 1924.

1. A PACKAGE OF RELATIVELY LOW PRESSURE, SELF-PROPELLING LIQUIDCOMPOSITION COMPRISING A FLUID-TIGHT CONTAINER HAVING CLOSURE MEANSPROVIDING A SMALL DISCHARGE ORIFICE FOR ATOMIZED DISPENSATION OFCONTENTS AND A VALVE-CONTROLLED PASSAGE LEADING TO SAID DISCHARGEORIFICE FROM THE INTERIOR OF SAID CONTAINER AT A POINT OF IMMERSION INTHE LIQUID COMPOSITION, SAID CONTAINER CONFINING THEREIN A BODY OFLIQUID COMPOSITION FOR DELIVERY THROUGH THE ORIFICE IN LIQUID PHASECONSISTING ESSENTIALLY OF A LIQUID MIXTURE OF DISPERSABLE PRODUCTSOLUTION AND VOLATILE PROPELLANT AND BEING OF THE PROPELLANT-IN-PRODUCTTYPE WHICH IMMEDIATELY UPON ORIFICE DELIVERY WILL BE CONVERTED TO ANATOMIZED MIST BY CHANGE OF THE CONTAINED PROPELLANT FROM LIQUID TOGASEOUS PHASE, THE BODY OF LIQUID COMPOSITION BEING CONFINED IN THECONTAINER UNDER A VAPOR PRESSURE OF THE PROPELLANT UP TO 25 P.S.I.G. AT70* F.; SAID DISPENSABLE PRODUCT SOLUTION BEING CHIEFLY AWATER-CONTAINING ALCOHOLIC MEDIUM OF SATURATED ALIPHATIC MONOHYDRICALCOHOL SELECTED FROM THE GROUP CONSISTING OF METHANOL, ETHANOL,ISOPROPANOL AND ITS EQUIVALENT PROPANOL, AND MIXTURES THEREOF, HAVING AWATER CONCENTRATION GREATER THAN 3% BY VOLUME, THE ALCOHOL CONCENTRATIONOF SAID ALCOHOLIC MEDIUM BEING BY VOLUME FROM ABOUT 75% TO ABOUT 88% FORISOPROPANOL AND ITS EQUIVALENT PROPANOL, FROM ABOUT 85% TO ABOUT 95% FORETHANOL AND FROM ABOUT 90% TO ABOUT 96.5% FOR METHANOL; SAID PROPELLANTBEING SELECTED FROM THOSE OF THE GROUP CONSISTING OF FLUORINATED LOWMOLECULAR WEIGHT SATURATED ALIPHATIC HYDROCARBONS HAVING A CARBONCONTENT OF C1-C2, CHLORINATED AND FLUORINATED LOW MOLECULAR WEIGHTSATURATED ALIPHATIC HYDROCARBONS HAVING A CARBON CONTENT OF C1-C2,NORMAL BUTANE, AND MIXTURES THEREOF, WHICH HAVE A BOILING POINT AT ONEATMOSPHERE LOWER THAN NORMAL ROOM TEMPERATURES AND A VAPOR PRESSURE UPTO 25 P.S.I.G. AT 70* F.; SAID PROPELLANT BEING PRESENT IN SAID LIQUIDCOMPOSITION IN AN AMOUNT UP TO 50% BY VOLUME THEREOF AND FROM ABOUT 69%BY VOLUME OF THAT QUANTITY WHICH PROVIDES A SATURATED SOLUTION OF THEALCO-